WO2024073001A1 - Réduction d'oxyde et d'hydroxyde de métal alcalin dans le film par couche passivée de surface ex situ - Google Patents

Réduction d'oxyde et d'hydroxyde de métal alcalin dans le film par couche passivée de surface ex situ Download PDF

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Publication number
WO2024073001A1
WO2024073001A1 PCT/US2023/034042 US2023034042W WO2024073001A1 WO 2024073001 A1 WO2024073001 A1 WO 2024073001A1 US 2023034042 W US2023034042 W US 2023034042W WO 2024073001 A1 WO2024073001 A1 WO 2024073001A1
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film
passivation layer
anode
lithium
metal
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PCT/US2023/034042
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English (en)
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Thomas Humphreys
Girish Kumar Gopalakrishnan Nair
Subramanya P. Herle
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Applied Materials, Inc.
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Publication of WO2024073001A1 publication Critical patent/WO2024073001A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0407—Methods of deposition of the material by coating on an electrolyte layer
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0421—Methods of deposition of the material involving vapour deposition
    • H01M4/0423—Physical vapour deposition
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/381—Alkaline or alkaline earth metals elements
    • H01M4/382—Lithium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • Embodiments of the present disclosure generally relate to metal electrodes, more specifically lithium-containing electrodes, high performance electrochemical devices, such as secondary batteries, including the aforementioned lithium-containing electrodes, and methods for fabricating the same.
  • metal electrodes more specifically lithium-containing electrodes
  • high performance electrochemical devices such as secondary batteries
  • methods for fabricating the same including the aforementioned lithium-containing electrodes, and methods for fabricating the same.
  • Description of the Related Art [0002] Rechargeable electrochemical storage systems are increasing in importance for many fields of everyday life.
  • High-capacity energy storage devices such as lithium-ion (Li-ion) batteries and capacitors
  • Li-ion lithium-ion
  • UPS uninterruptible power supply
  • the charge/discharge time and capacity of energy storage devices are key parameters.
  • the size, weight, and/or cost of such energy storage devices are also key parameters.
  • low internal resistance is beneficial for high performance. The lower the resistance, the less restriction the energy storage device encounters in delivering electrical energy. For example, in the case of a battery, internal resistance affects performance by reducing the total amount of useful energy stored by the battery as well as the ability of the battery to deliver high current.
  • Li-ion batteries are thought to have the best chance at achieving the sought after capacity and cycling.
  • Li-ion batteries as currently constituted often lack the energy capacity and number of charge/discharge cycles for these growing applications.
  • PATENT Attorney Docket No.: 44020676WO01 SUMMARY [0005]
  • an anode for a battery is disclosed.
  • the anode includes a substrate, a metal film disposed on the substrate, and a solid electrolyte interphase (SEI) film stack disposed on the metal film.
  • the SEI film stack includes a first passivation layer disposed on the metal film and a second passivation layer disposed on the first passivation layer.
  • an energy storage device includes a cathode, a separator film, and an anode.
  • the cathode includes a cathode current collector and a cathode film disposed on the cathode current collector.
  • the separator film disposed on the cathode film.
  • the anode is disposed on the separator film.
  • the anode includes an anode film disposed on the separator film, a solid electrolyte interphase (SEI) film stack disposed on the anode film, and an anode current collector disposed on the anode film.
  • the SEI film stack includes a first passivation layer disposed on the anode film and a second passivation layer disposed on the first passivation layer.
  • a method of forming an anode for a battery includes disposing a metal film over a substrate and disposing a solid electrolyte interphase (SEI) film stack over the metal film.
  • the disposing of the SEI film stack includes disposing a first film over the metal film and disposing a second film over the first film.
  • the first film is a lithium carbonate film.
  • the second film is a lithium halide film.
  • Figure 2 is a schematic, cross-sectional view of a dual-sided anode electrode, according to embodiments.
  • Figure 3 is a schematic, cross-sectional view of a dual-sided anode electrode, according to embodiments.
  • Figure 4 is a schematic cross-sectional view of a metal anode, according to embodiments.
  • Figure 5 is a flow diagram of a method of forming a metal anode, according to embodiments.
  • Figure 6A-6F are schematic, cross-sectional views of a portion of a metal anode during a method of forming the metal anode, according to embodiments.
  • Figure 7 is a schematic view of an integrated processing tool for forming a metal anode, according to embodiments.
  • Figure 8 is a flow diagram of a method of forming a metal anode using a transfer substrate, according to embodiments.
  • Figure 9A-9B are graphs illustrating the X-Ray Photoelectron Spectroscopy (XPS) depth profiling of an SEI film stack lithium anode sample, according to embodiments.
  • Figure 10 illustrates a modified interface metal anode, according to embodiments.
  • identical reference numerals have been used, where possible, to designate identical elements that are common to the figures.
  • Embodiments described herein will be described below in reference to a roll-to-roll coating system. Other tools capable of performing high rate deposition processes may also be adapted to benefit from the embodiments described herein. In addition, any system enabling the deposition processes described herein can be used to advantage.
  • the apparatus description described herein is illustrative and should not be construed or interpreted as limiting the scope of the embodiments described herein. It should also be understood that although described as a roll-to- roll process, the embodiments described herein may also be performed on discrete substrates.
  • Development of rechargeable lithium metal batteries is considered a promising technology, which can enable a high-energy-density system for energy storage.
  • the organic solvent is decomposed and forms the SEI film at first charge.
  • a lithium was deposited and the lithium growth was attributed to “bottom growth.”
  • a concentration gradient in the electrolyte causes ‘tip growth’ and this tip growth causes shorting of the cell.
  • the SEI film that forms on the anode is typically a mixture of lithium oxide, lithium halides, and semicarbonates. Initially, the SEI film is electrically insulating yet sufficiently conductive to lithium ions.
  • the SEI prevents decomposition of the electrolyte after the second charge.
  • the SEI can be thought of as a three-layer system with two key interfaces. In conventional electrochemical studies, it is often referred to as an electrical double layer. In its simplest form, an anode coated by an SEI will undergo three stages when charged.
  • These three stages include electron transfer between the anode (M) and the SEI (M 0 – ne ⁇ M n+ M/SEI ); cation migration from the anode-SEI interface to the SEI-electrolyte (E) interface (M n+ M/SEI ⁇ M n+ SEI/E ); and cation transfer in the SEI to electrolyte at the SEI/electrolyte interface (E(solv) + M n+ SEI/E ⁇ M n+ E(solv)).
  • the power density and recharge speed of the battery is dependent on how quickly the anode can release and gain charge.
  • Lithium ion exchange at the SEI is a multi-stage process and as with most multi-stage processes, the speed of the entire process is dependent upon the slowest stage.
  • the anion migration may be the bottleneck for most systems.
  • the diffusive characteristics of the solvents may dictate the speed of migration between the anode- SEI interface and the SEI-electrolyte (E) interface.
  • E SEI-electrolyte
  • the SEI may thicken when cycled, slowing diffusion from the Electrode/SEI interface to the SEI/Electrolyte.
  • alkyl carbonates in the PATENT Attorney Docket No.: 44020676WO01 electrolyte decompose into insoluble Li 2 CO 3 , which may increase the thickness of the SEI film, clog pores of the SEI film, and limit lithium ion access to the anode.
  • SEI growth may also occur by gas evolution at the cathode and particle migration towards the anode, increasing impedance and decreasing capacity. Further, the randomness of metallic lithium embedded in the anode during intercalation may result in dendrite formation.
  • Embodiments of the present disclosure relate to constructing a stable and an efficient SEI film ex-situ.
  • the SEI film is formed in the energy storage device during fabrication of the energy storage device.
  • This new and efficient SEI film is believed to inhibit lithium dendrite growth and thus achieves superior lithium metal cycling performance relative to current lithium based anodes, which rely on an in-situ SEI film.
  • Figure 1 illustrates a cross-sectional view of one embodiment of an energy storage device 100 incorporating an anode electrode structure having an SEI film stack 140 formed according to embodiments described herein.
  • the energy storage device 100 is a rechargeable battery cell. In some embodiments, the energy storage device 100 is combined with other cells to form a rechargeable battery.
  • the energy storage device 100 has a cathode 105, an anode 145, and a separator film 130.
  • the cathode 105 includes a cathode current collector 110 and a cathode film 120.
  • the anode 145 includes the SEI film stack 140, an anode film 150, and an anode current collector 160.
  • the SEI film stack 140 can have more than one layer, for example, a lithium carbonate film in combination with lithium fluoride (LiF).
  • portions of the SEI film stack 140 are formed by exposing a lithium film to an SF 6 gas treatment to form LiF and Li 2 S portions of the SEI film stack 140 on the surface of the lithium film.
  • the SF 6 gas can be activated to react with the exposed lithium surface either thermally or SF 6 gas can be plasma PATENT Attorney Docket No.: 44020676WO01 activated.
  • the thickness of the SEI film stack 140 can be controlled by modifying the SF 6 gas exposure time and temperature.
  • the cathode current collector 110 and anode current collector 160, on the cathode film 120 and the anode film 150, respectively, can be identical or different electronic conductors.
  • cathode current collector 110 and anode current collector 160 may be comprised of include aluminum (Al), copper (Cu), zinc (Zn), nickel (Ni), cobalt (Co), tin (Sn), silicon (Si), manganese (Mn), magnesium (Mg), alloys thereof, and combinations thereof.
  • at least one of the current collectors 110, 160 is perforated.
  • current collectors may be of any form factor (e.g., metallic foil, sheet, or plate), shape and micro/macro structure.
  • at least one of the current collectors 110, 160 include a polyethylene terephthalate (“PET”) film coated with a metallic material.
  • PET polyethylene terephthalate
  • the anode current collector 160 is a PET film coated with copper. In another embodiment, the anode current collector 160 is a multi-metal layer on PET. The multi-metal layer can be combinations of copper, chromium, nickel, etc. In one embodiment, the anode current collector 160 is a multi-layer structure that includes a copper-nickel cladding material. In one embodiment, the multi-layer structure includes a first layer of nickel or chromium, a second layer of copper formed on the first layer, and a third layer including nickel, chromium, or both formed on the second layer. In one embodiment, the anode current collector 160 is nickel coated copper.
  • current collectors may be of any form factor (e.g., metallic foil, sheet, or plate), shape and micro/macro structure. Generally, in prismatic cells, tabs are formed of the same material as the current collector and may be formed during fabrication of the stack, or added later. All components except current collectors 110 and 160 contain lithium ion electrolytes.
  • the cathode current collector 110 is aluminum.
  • the cathode current collector 110 has a thickness from about 0.5 ⁇ m to about 20 ⁇ m (e.g., from about 1 ⁇ m to about 10 ⁇ m; from about 5 ⁇ m to about 10 ⁇ m).
  • the anode current collector 160 is copper.
  • the anode current collector 160 has a thickness from about 0.5 ⁇ m to about 20 ⁇ m (e.g., from about 1 ⁇ m to about 10 ⁇ m; from about 2 ⁇ m to about 8 ⁇ m; from about 5 ⁇ m to about 10 ⁇ m).
  • PATENT Attorney Docket No.: 44020676WO01 [0031]
  • the anode film 150 or anode may be any material compatible with the cathode film 120 or cathode.
  • the anode film 150 may have an energy capacity greater than or equal to 372 mAh/g, preferably ⁇ 700 mAh/g, and most preferably ⁇ 1000 mAh/g.
  • the anode film 150 may be constructed from lithium metal, lithium metal foil or a lithium alloy foil (e.g. lithium aluminum alloys), or a mixture of a lithium metal and/or lithium alloy and materials such as carbon (e.g. coke, graphite), nickel, copper, tin, indium, silicon, oxides thereof, or combinations thereof.
  • the anode film 150 typically comprises intercalation compounds containing lithium or insertion compounds containing lithium.
  • the lithium metal may be deposited using the methods described herein.
  • the anode film 150 may be formed by extrusion, physical or chemical thin-film techniques, such as sputtering, electron beam evaporation, chemical vapor deposition (CVD), three-dimensional printing, lithium powder deposition, etc.
  • the anode film 150 has a thickness from about 0.5 ⁇ m to about 20 ⁇ m (e.g., from about 1 ⁇ m to about 10 ⁇ m; from about 5 ⁇ m to about 10 ⁇ m).
  • the anode film 150 is a lithium metal or lithium metal alloy film.
  • the SEI film stack 140 is formed ex-situ on the anode film 150.
  • the SEI film stack 140 is electrically insulating yet sufficiently conductive to lithium-ions.
  • the SEI film stack 140 is a nonporous film. In another embodiment, the SEI film stack 140 is a porous film. In one embodiment, the SEI film stack 140 has a plurality of nanopores that are sized to have an average pore size or diameter less than about 10 nanometers (e.g., from about 1 nanometer to about 10 nanometers; from about 3 nanometers to about 5 nanometers). In another embodiment, the SEI film stack 140 has a plurality of nanopores that are sized to have an average pore size or diameter less than about 5 nanometers.
  • the SEI film stack 140 has a plurality of nanopores having a diameter ranging from about 1 nanometer to about 20 nanometers (e.g., from about 2 nanometers to about 15 nanometers; or from about 5 nanometers to about 10 nanometers).
  • the SEI film stack 140 may be a coating or a discrete layer, either having a thickness in the range of 1 nanometer to 200 nanometers (e.g., in the range of 5 nanometers to 200 nanometers; in the range of 10 nanometers to 50 nanometers).
  • PATENT Attorney Docket No.: 44020676WO01 Not to be bound by theory, but it is believed that SEI films greater than 200 nanometers may increase resistance within the rechargeable battery.
  • Examples of materials that may be included in the SEI film stack 140 include, but are not limited to a chalcogenide film (e.g., CuS, Cu 2 Se, Cu 2 S, Cu 2 Te, CuTe, Bi 2 Te 3 , or Bi 2 Se 3 film) or composite chalcogenide film optionally in combination with at least one of a lithium carbonate (Li 2 CO 3 ) film, a lithium oxide (Li 2 O) film, a lithium nitride film (Li 3 N), and a lithium halide film (e.g. LiF, LiCl, LiBr, or LiI).
  • a chalcogenide film e.g., CuS, Cu 2 Se, Cu 2 S, Cu 2 Te, CuTe, Bi 2 Te 3 , or Bi 2 Se 3 film
  • composite chalcogenide film optionally in combination with at least one of a lithium carbonate (Li 2 CO 3 ) film, a lithium oxide (Li 2 O) film, a lithium nitride
  • the SEI film stack 140 can take-up Li- conducting electrolyte to form gel during device fabrication which is beneficial for forming good solid electrolyte interface (SEI) and also helps lower resistance.
  • Suitable methods for depositing portions of the SEI film stack 140 directly on the metal film include, but are not limited to, Physical Vapor Deposition (PVD), such as evaporation or sputtering, a slot-die process, a thin-film transfer process, or a three- dimensional lithium printing process.
  • Portions of the SEI film stack may be formed by plasma treatment of previously deposited layers (e.g., oxygen plasma treatment of an exposed lithium surface to form a lithium oxide film).
  • the cathode film 120 or cathode may be any material compatible with the anode and may include an intercalation compound, an insertion compound, or an electrochemically active polymer.
  • Suitable intercalation materials include, for example, lithium-containing metal oxides, MoS 2 , FeS 2 , MnO 2 , TiS 2 , NbSe 3 , LiCoO 2 , LiNiO 2 , LiMnO 2 , LiMn 2 O 4 , V 6 O 13 , and V 2 O 5 .
  • Suitable polymers include, for example, polyacetylene, polypyrrole, polyaniline, and polythiophene.
  • the cathode film 120 or cathode may be made from a layered oxide, such as lithium cobalt oxide, an olivine, such as lithium iron phosphate, or a spinel, such as lithium manganese oxide.
  • Exemplary lithium-containing oxides may be layered, such as lithium cobalt oxide (LiCoO 2 ), or mixed metal oxides, such as LiNi x Co 1-2x MnO 2 , LiNiMnCoO 2 (“NMC”), LiNi 0.5 Mn 1.5 O 4 , Li(Ni 0.8 Co 0.15 Al 0.05 )O 2 , LiMn 2 O 4 , and doped lithium rich layered-layered materials, wherein x is zero or a non-zero number.
  • Exemplary phosphates may be iron olivine (LiFePO 4 ) and it is variants (such as LiFe (1-x) Mg x PO 4 , wherein x is between 0 and 1), LiMoPO 4 , LiCoPO 4 , LiNiPO 4 , Li 3 V 2 (PO 4 ) 3 , LiVOPO 4 , LiMP 2 O 7 , or LiFe 1.5 P 2 O 7 , wherein x is zero or a non-zero number.
  • Exemplary fluorophosphates may be LiVPO 4 F, LiAlPO 4 F, Li 5 V(PO 4 ) 2 F 2, Li 5 Cr(PO 4 ) 2 F 2, Li 2 CoPO 4 F, or Li 2 NiPO 4 F.
  • Exemplary silicates may be Li 2 FeSiO 4 , Li 2 MnSiO 4 , or Li 2 VOSiO 4 .
  • An exemplary non- lithium compound is Na 5 V 2 (PO 4 ) 2 F 3 .
  • the cathode film 120 may be formed by physical or chemical thin-film techniques, such as sputtering, electron beam evaporation, chemical vapor deposition (CVD), etc.
  • the cathode film 120 has a thickness from about 10 ⁇ m to about 100 ⁇ m (e.g., from about 30 ⁇ m to about 80 ⁇ m; or from about 40 ⁇ m to about 60 ⁇ m).
  • the cathode film 120 is a LiCoO 2 film. In another embodiment, the cathode film 120 is an NMC film.
  • the separator film 130 comprises a porous (e.g., microporous) polymeric substrate capable of conducting ions (e.g., a separator film) with pores.
  • the porous polymeric substrate itself does not need to be ion conducting, however, once filled with electrolyte (liquid, gel, solid, combination etc.), the combination of porous substrate and electrolyte is ion conducting.
  • the porous polymeric substrate is a multi-layer polymeric substrate. In one embodiment, the pores are micropores.
  • the porous polymeric substrate consists of any commercially available polymeric microporous membranes (e.g., single-ply or multi-ply), for example, those products produced by Polypore (Celgard Inc., of Charlotte, North Carolina), Toray Tonen (Battery separator film (BSF)), SK Energy (Li-ion battery separator (LiBS), Evonik industries (SEPARION® ceramic separator membrane), Asahi Kasei (HiporeTM polyolefin flat film membrane), DuPont (Energain®), etc.
  • the porous polymeric substrate has a porosity in the range of 20 to 80% (e.g., in the range of 28 to 60%).
  • the porous polymeric substrate has an average pore size in the range of 0.02 to 5 microns (e.g., 0.08 to 2 microns). In some embodiments, the porous polymeric substrate has a Gurley Number in the range of 15 to 150 seconds (Gurley Number refers to the time it takes for 10 cc of air at 12.2 inches of water to pass through one square inch of membrane). In some embodiments, the porous polymeric substrate is polyolefinic. Exemplary polyolefins include polypropylene, polyethylene, or combinations thereof.
  • lithium is contained in the metal film of the anode electrode, and lithium manganese oxide (LiMnO4) or lithium cobalt oxide (LiCoO2) at the cathode electrode, for example, although in some embodiments, the anode electrode may also include PATENT Attorney Docket No.: 44020676WO01 lithium absorbing materials such as silicon, tin, etc.
  • the energy storage device even though shown as a planar structure, may also be formed into a cylinder by rolling the stack of layers; furthermore, embodiments of the present disclosure also contemplate other cell configurations (e.g., prismatic cells, button cells).
  • Electrolytes infused in cell components can be comprised of a liquid/gel or a solid polymer and may be different in each.
  • the electrolyte primarily includes a salt and a medium (e.g., in a liquid electrolyte, the medium may be referred to as a solvent; in a gel electrolyte, the medium may be a polymer matrix).
  • the salt may be a lithium salt.
  • the lithium salt may include, for example, LiPF 6 , LiAsF 6 , LiCF 3 SO 3 , LiN(CF 3 SO 3 ) 3 , LiBF 6 , and LiClO 4 , lithium bistrifluoromethanesulfonimidate (e.g., LiTFSI), BETTE electrolyte (commercially available from 3M Corp. of Minneapolis, MN) and combinations thereof.
  • LiPF 6 LiAsF 6
  • LiCF 3 SO 3 LiN(CF 3 SO 3 ) 3
  • LiBF 6 LiClO 4
  • Li bistrifluoromethanesulfonimidate e.g., LiTFSI
  • BETTE electrolyte commercially available from 3M Corp. of Minneapolis, MN
  • Solvents may include, for example, ethylene carbonate (EC), propylene carbonate (PC), EC/PC, 2-MeTHF(2-methyltetrahydrofuran)/EC/PC, EC/DMC (dimethyl carbonate), EC/DME (dimethyl ethane), EC/DEC (diethyl carbonate), EC/EMC (ethyl methyl carbonate), EC/EMC/DMC/DEC, EC/EMC/DMC/DEC/PE, PC/DME, and DME/PC.
  • Polymer matrices may include, for example, PVDF (polyvinylidene fluoride), PVDF:THF (PVDF:tetrahydrofuran), PVDF:CTFE (PVDF: chlorotrifluoroethylene) PAN (polyacrylonitrile), and PEO (polyethylene oxide).
  • FIG 2 illustrates a cross-sectional view of one embodiment of a dual- sided anode electrode structure 200 having a solid electrolyte interphase (SEI) film stack 240a, 240b (collectively 240) formed according to embodiments described herein.
  • SEI solid electrolyte interphase
  • the SEI film stack 240a, 240b may be used in place of the SEI film stack 140 depicted in Figure 1.
  • Each SEI film stack 240a, 240b includes a first passivation layer and a second passivation layer.
  • the first passivation layer includes is disposed on the anode film 150a, 150b.
  • the first passivation layer includes a lithium carbonate layer.
  • the second passivation layer is disposed on the first passivation layer.
  • the second passivation layer includes a dielectric film.
  • the dielectric film may include a lithium halide, such as LiF, LiCl, LiBr, or LiI.
  • FIG. 3 illustrates a cross-sectional view of another embodiment of a dual- sided anode electrode structure 300 having a solid electrolyte interphase (SEI) film stack 340a, 340b (collectively 340) formed according to embodiments described herein.
  • the dual-sided anode electrode structure 300 may be used in place of the anode 145 depicted in Figure 1.
  • the SEI film stack 340a, 340b may be used in place of the SEI film stack 140 depicted in Figure 1.
  • Each SEI film stack 340a, 340b includes a third passivation layer.
  • the third passivation layer includes a lithium oxide film 210a, 210b respectively disposed over each anode film 150a, 150b.
  • Each SEI film stack 340a, 340b further includes a first passivation layer disposed over the lithium oxide film 210a, 210b.
  • the first passivation layer includes lithium carbonate film 310a, 310b (collectively 310).
  • Each SEI film stack 340a, 340b further includes a second passivation layer disposed over the first passivation layer.
  • the second passivation layer includes a dielectric film (e.g., lithium halide film 320a, 320b) (collectively 320).
  • FIG. 2 & 3 illustrates an embodiment of a metal anode 400 of an energy storage device 100.
  • the metal anode 400 includes a substrate 460, a metal film 450, and a SEI film stack 440.
  • the metal film 450 is the anode film 150 and the substrate 460 is the anode current collector 160. In some embodiments, the metal film is a metal film. In some embodiments, the metal film comprises a metal or a metal alloy, such as lithium. In one embodiment, the metal film 450 is disposed over a copper substrate 460. In some embodiments, if an anode film 150 is already present on the substrate 460, the metal film 450 is disposed over the anode film 150. If the anode film 150 is not present, the metal film 450 may be disposed directly on the substrate 460. Any suitable metal deposition process for depositing thin films of metal may be used to deposit the metal film 450.
  • Deposition of the metal film 450 may be by evaporation, a sputtering process, a slot-die process, a transfer process, or a three-dimensional lithium printing process.
  • the chamber for depositing the thin PATENT Attorney Docket No.: 44020676WO01 film of metal may include a PVD system, an electron-beam evaporator, a thermal evaporator, a thin film transfer system (including large area pattern printing systems such as gravure printing systems) or a slot-die deposition system.
  • the metal film 450 has a thickness of 100 micrometers or less (e.g., from about 1 ⁇ m to about 100 ⁇ m; from about 3 ⁇ m to about 30 ⁇ m; from about 20 ⁇ m to about 30 ⁇ m; from about 1 ⁇ m to about 20 ⁇ m; or from about 50 ⁇ m to about 100 ⁇ m).
  • the substrate 402 has a thickness between about 10 ⁇ m and about 100 ⁇ m, such as about 18 ⁇ m.
  • the SEI film stack 440 further includes at least a first passivation layer and a second passivation layer.
  • the SEI film stack includes materials that are electrically insulating (e.g., dielectric materials) and ionically conducting.
  • the first passivation layer is the lithium carbonate (Li 2 CO 3 ) film 310 and the second passivation layer is the lithium halide film 320.
  • the first passivation layer may include a lithio-philic material.
  • the first passivation layer may also include a dielectric material (e.g., an electrically insulating material).
  • the second passivation layer may include a dielectric material (e.g., an electrically insulating material).
  • the lithium halide film may include e.g. LiF, LiCl, LiBr, or LiI.
  • the SEI film stack 440 includes a third passivation layer between the lithium carbonate film 310 and the metal film 450.
  • the lithium carbonate film 310 has a thickness of about 200 nm or less (e.g., from about 5 nm to about 200 nm; from about 20 nm to about 150 nm; from about 40 nm to about 100 nm; from about 60 nm to about 80 nm).
  • the lithium halide film 320 has a thickness of about 15 nm or less (e.g., from about 1 nm to about 15 nm; from about 5 to about 10 nm; from about 10 nm to about 15 nm).
  • the first passivation layer and second passivation layer are not distinct layers.
  • the lithium carbonate layer and the lithium halide layer have a blended region at the interface of the lithium carbonate and lithium halide.
  • the first passivation layer and third passivation layer are not distinct layers.
  • the lithium carbonate layer and the lithium oxide layer have a blended region at the interface of the lithium carbonate and lithium oxide.
  • the exposure to CO 2 leads to the formation of a lithium carbonate film 310 on the metal film 450.
  • the lithium halide film 320 is deposited onto the lithium carbonate film 310.
  • the deposition of the lithium halide film 320 can be done using one of, sputter deposition, electron beam evaporation, ion beam deposition, or resistive thermal evaporation.
  • Figure 5 is a flow diagram of a method 500 of forming a anode 400 of an energy storage device 100, as shown in Figure 4.
  • Figures 6A-6F are schematic, cross-sectional views of the anode 400 during the method of forming an anode 400.
  • a metal film 450 is disposed over the substrate 460 as shown in Figure 6A.
  • the metal film 450 is the anode film 150 and the substrate 460 is the anode current collector 160.
  • the substrate 460 is a continuous sheet of material.
  • the substrate 460 includes one of aluminum (Al), copper (Cu), zinc (Zn), nickel (Ni), cobalt (Co), manganese (Mn), chromium (Cr), stainless steel, clad materials, alloys thereof, and combinations thereof.
  • the substrate 460 is perforated.
  • the substrate 460 may be of any form factor (e.g., metallic foil, sheet, or plate), shape and micro/macro structure.
  • the metal film 450 is deposited on the substrate 460 using a flexible substrate coating apparatus 700, which is describe with respect to Figure 7.
  • the copper substrate 460 is fed through the flexible substrate coating apparatus 700, where lithium is thermally evaporated onto the copper substrate 460 to create the metal film 450.
  • the metal film 450 is disposed over the anode film 150. If the anode film 150 is not present, the metal film 450 may be disposed directly on the substrate 460. Any suitable metal film deposition process for depositing thin films of metal may be used to deposit the metal film 450. Deposition of the metal film 450 may be by PATENT Attorney Docket No.: 44020676WO01 evaporation, a sputtering process, a slot-die process, a transfer process, or a three- dimensional lithium printing process.
  • the chamber for depositing the metal film 450 may include a PVD system, an electron-beam evaporator, a thermal evaporator, a thin film transfer system (including large area pattern printing systems such as gravure printing systems) or a slot-die deposition system.
  • the metal film 450 has a thickness of 100 micrometers or less (e.g., from about 1 ⁇ m to about 100 ⁇ m; from about 3 ⁇ m to about 30 ⁇ m; from about 20 ⁇ m to about 30 ⁇ m; from about 1 ⁇ m to about 20 ⁇ m; or from about 50 ⁇ m to about 100 ⁇ m).
  • a transfer substrate could be used.
  • the transfer substrate could be flexible plastic film (e.g., polyethylene terephthalate (PET), polyethylene (PE), polypropylene (PP), polyimide (PI), etc.).
  • the transfer substrate may be coated with an organic or inorganic functional layer or layers which may be selectively transferred or aid selective transfer of metal film (e.g., PDMS, boron nitride, aluminum oxide (AlO x ), polytetrafluoroethylene (PTFE), fluorinated ethylene propylene (FEP), perfluorooctanoic acid (PFOA), polyvinylidene (PVDF), etc.).
  • metal film e.g., PDMS, boron nitride, aluminum oxide (AlO x ), polytetrafluoroethylene (PTFE), fluorinated ethylene propylene (FEP), perfluorooctanoic acid (PFOA), polyvinylidene (PVDF), etc.
  • the metal and dielectric layers are then deposited onto this plastic substrate and subsequently transferred by lamination onto the desired device architecture, such as a current collector or substrate 460 (e.g., copper (Cu) and metallized plastic such as cu on PET).
  • the transfer substrate has a thickness of 200 microns or less, such as from 5 microns to about 100 microns, from about 10 microns to about 75 microns, or from about 20 microns to about 50 microns.
  • the substrate 460 is exposed to a pretreatment process, which includes at least one of a plasma treatment or corona discharge process to remove organic materials from the exposed surfaces of the substrate 460. The pretreatment process is performed prior to film deposition on the substrate 460.
  • an SEI film stack 440 is disposed over the metal film 450.
  • the SEI film stack 440 includes a lithium carbonate (Li 2 CO 3 ) film and lithium halide film.
  • Operation 504 may be divided into optional operation 506, operation 508, and operation 510.
  • a lithium oxide (Li 2 O) film 210 is disposed over the metal film 450.
  • the lithium oxide film 210 has a thickness of 500 nanometers or less (e.g., from about 1 nm to about 400 nm; from about 25 nm PATENT Attorney Docket No.: 44020676WO01 to about 300 nm; from about 50 nm to about 200 nm; or from about 100 nm to about 150 nm).
  • the lithium oxide film 210 is formed by depositing an additional metal film via PVD in an oxygen-containing atmosphere.
  • a first passivation layer is disposed over the metal film 450, as shown in Figure 6C.
  • the first passivation layer includes a lithium carbonate film 310.
  • the lithium carbonate film 310 has a thickness of about 200 nm or less (e.g., from about 5 nm to about 200 nm; from about 20 nm to about 150 nm; from about 40 nm to about 100 nm; from about 60 nm to about 80 nm).
  • the lithium carbonate (Li 2 CO 3 ) film is disposed over a third passivation layer.
  • the third passivation layer is a lithium oxide film 210, as shown in Figure 6D.
  • the lithium carbonate film 310 has a thickness of about 200 nm or less (e.g., from about 5 nm to about 200 nm; from about 20 nm to about 150 nm; from about 40 nm to about 100 nm; from about 60 nm to about 80 nm).
  • the lithium carbonate film 310 is formed by depositing an additional metal film on the lithium oxide film 210 and exposing the metal film 450 to a plasma process (e.g., gas treatment using at least one of O 2 and CO 2 ) to oxidize the metal film 450.
  • the lithium oxide film 210 is formed by depositing an additional metal film via PVD in an oxygen-and-carbon-containing atmosphere.
  • a second passivation layer is disposed over the lithium carbonate film 310, as shown in Figure 6E.
  • the second passivation layer includes a dielectric layer, such as a lithium halide film 320.
  • the lithium halide film is selected from LiF, LiCl, LiBr, and LiI.
  • the lithium halide film 320 is a lithium fluoride film.
  • the lithium halide film 320 is deposited on the lithium carbonate film 310 by Physical Vapor Deposition (PVD), evaporation, atomic layer deposition (ALD), a slot-die process, a thin-film transfer process, or a three-dimensional lithium printing process.
  • PVD is the method for deposition of the lithium halide film 320.
  • the lithium halide film 320 is deposited using a thermal evaporation process.
  • PATENT Attorney Docket No.: 44020676WO01 the lithium halide film is formed by reduction of a functional layer or surface functional groups on the plastic substrate used for metal deposition.
  • the lithium halide film 320 has a thickness of about 15 nm or less (e.g., from about 1 nm to about 15 nm; from about 5 to about 10 nm; from about 10 nm to about 15 nm).
  • the lithium halide film 320 is disposed over the lithium carbonate (Li2CO3) film 310, which is disposed over the lithium oxide film 210, as shown in Figure 6F.
  • the lithium halide film 320 is deposited on the lithium carbonate film 310 by Physical Vapor Deposition (PVD), evaporation, atomic layer deposition (ALD), a slot-die process, a thin-film transfer process, or a three- dimensional lithium printing process.
  • PVD is the method for deposition of the lithium halide film 320.
  • the lithium halide film 320 is deposited using a thermal evaporation process.
  • the lithium halide film 320 has a thickness of about 15 nm or less (e.g., from about 1 nm to about 15 nm; from about 5 to about 10 nm; from about 10 nm to about 15 nm).
  • FIG. 7 illustrates a schematic view of a flexible substrate coating apparatus 700 for forming anode electrode structures according to embodiments described herein.
  • the flexible substrate coating apparatus 700 can be used for manufacturing lithium anodes, and particularly for SEI film stacks 440 for anode 400.
  • the flexible substrate coating apparatus 700 is constituted as a roll-to-roll system including an unwinding module 702, a processing module 704 and a winding module 706.
  • the processing module 704 comprises a plurality of processing modules or chambers 710, 720, 730 and 740 arranged in sequence, each configured to perform one processing operation to the continuous sheet of material 750 or web of material.
  • the processing chambers 710-740 are radially disposed about a coating drum 755. Arrangements other than radial are contemplated.
  • the processing chambers may be positioned in a linear configuration.
  • the processing chambers 710-740 are stand-alone modular processing chambers wherein each modular processing chamber is structurally separated from the other modular processing chambers.
  • each of the stand-alone modular processing chambers can be arranged, rearranged, replaced, or maintained independently without affecting each other.
  • the processing chambers 710-740 may include any suitable structure, configuration, arrangement, and/or components that enable the flexible substrate coating apparatus 700 to deposit an anode according to embodiments of the present disclosure.
  • the processing chambers may include suitable deposition systems including coating sources, power sources, individual pressure controls, deposition control systems, and temperature control.
  • the chambers are provided with individual gas supplies. The chambers are typically separated from each other to provide good gas separation.
  • the flexible substrate coating apparatus 700 is not limited in the number of deposition chambers.
  • flexible substrate coating apparatus 700 may include 3, 6, or 12 processing chambers.
  • the processing chambers 710-740 typically include one or more deposition units 712, 722, 732, and 742.
  • the one or more deposition units as described herein can be selected from the group of a CVD or ALD source, a PECVD source, and a PVD source.
  • the one or more deposition units can include an evaporation source, a sputter source, such as, a magnetron sputter source, a DC sputter source, an AC sputter source, a pulsed sputter source, a radio frequency (RF) sputtering source, or a middle frequency (MF) sputtering source.
  • a sputter source such as, a magnetron sputter source, a DC sputter source, an AC sputter source, a pulsed sputter source, a radio frequency (RF) sputtering source, or a middle frequency (MF) sputtering source.
  • RF radio frequency
  • MF middle frequency
  • the one or more deposition units can include an evaporation PATENT Attorney Docket No.: 44020676WO01 source.
  • the evaporation source is a thermal evaporation source or an electron beam evaporation source.
  • the evaporation source is a lithium (Li) source.
  • the evaporation source may also be an alloy of two or more metals.
  • the material to be deposited e.g., lithium
  • the lithium can be provided in a crucible.
  • the lithium can, for example, be evaporated by thermal evaporation techniques or by electron beam evaporation techniques.
  • any of the processing chambers 710-740 of the flexible substrate coating apparatus 700 may be configured for performing deposition by sputtering, such as magnetron sputtering.
  • magnet sputtering refers to sputtering performed using a magnet assembly, that is, a unit capable of a generating a magnetic field.
  • a magnet assembly typically includes a permanent magnet.
  • This permanent magnet is typically arranged within a rotatable target or coupled to a planar target in a manner such that the free electrons are trapped within the generated magnetic field generated below the rotatable target surface.
  • Such a magnet assembly may also be arranged coupled to a planar cathode.
  • Magnetron sputtering may also be realized by a double magnetron cathode, such as, but not limited to, a TwinMagTM cathode assembly.
  • the cathodes in the processing chamber may be interchangeable.
  • a modular design of the apparatus is provided which facilitates optimizing the apparatus for particular manufacturing processes.
  • the number of cathodes in a chamber for sputtering deposition is chosen for optimizing an optimal productivity of the flexible substrate coating apparatus 700.
  • one or some of the processing chambers 710-740 may be configured for performing sputtering without a magnetron assembly.
  • one or some of the chambers may be configured for performing deposition by other methods, such as, but not limited to, chemical vapor deposition, atomic laser deposition or pulsed laser deposition.
  • one or some of the chambers may be configured for performing a plasma treatment process, such as a plasma oxidation or plasma nitridation process.
  • the processing chambers 710-740 are configured to process both sides of the continuous sheet of material 750.
  • the flexible PATENT Attorney Docket No.: 44020676WO01 substrate coating apparatus 700 is configured to process the continuous sheet of material 750, which is horizontally oriented, the flexible substrate coating apparatus may be configured to process substrates positioned in different orientations, for example, the continuous sheet of material 750 may be vertically oriented.
  • the continuous sheet of material 750 is a flexible conductive substrate.
  • the continuous sheet of material 750 includes a conductive substrate with one or more layers formed thereon.
  • the conductive substrate is a copper substrate.
  • the flexible substrate coating apparatus 700 comprises a transfer mechanism 752.
  • the transfer mechanism 752 may comprise any transfer mechanism capable of moving the continuous sheet of material 750 through the processing region of the processing chambers 710-740.
  • the transfer mechanism 752 may comprise a common transport architecture.
  • the common transport architecture may comprise a reel-to-reel system with a common take-up-reel 754 positioned in the winding module 706, the coating drum 755 positioned in the processing module 704, and a feed reel 756 positioned in the unwinding module 702.
  • the take-up reel 754, the coating drum 755, and the feed reel 756 may be individually heated.
  • the take-up reel 754, the coating drum 755 and the feed reel 756 may be individually heated using an internal heat source positioned within each reel or an external heat source.
  • the common transport architecture may further comprise one or more auxiliary transfer reels 753a, 753b positioned between the take-up reel 754, the coating drum 755, and the feed reel 756.
  • the flexible substrate coating apparatus 700 is depicted as having a single processing region, in certain embodiments, it may be advantageous to have separated or discrete processing regions for each individual processing chamber 710-740.
  • the common transport architecture may be a reel-to-reel system where each chamber or processing region has an individual take-up-reel and feed reel and one or more optional intermediate transfer reels positioned between the take-up reel and the feed reel.
  • the flexible substrate coating apparatus 700 may comprise the feed reel 756 and the take-up reel 754 for moving the continuous sheet of material 750 through the different processing chambers 710-740.
  • the first processing PATENT Attorney Docket No.: 44020676WO01 chamber 710 and the second processing chamber 720 are each configured to deposit a portion of a metal film.
  • the third processing chamber 730 is configured to deposit a lithium carbonate film.
  • the fourth processing chamber 740 is configured to deposit a lithium halide film over the lithium carbonate film.
  • the first processing chamber 710 is configured to deposit a copper film on the polymer material.
  • the second processing chamber 720 is configured to deposit a portion of a metal film.
  • the third processing chamber 730 is configured to deposit a lithium carbonate film.
  • the fourth processing chamber 740 is configured to deposit a lithium halide film.
  • the finished negative electrode will not be collected on the take-up reel 754 as shown in the figures, but may go directly for integration with the separator and positive electrodes, etc., to form battery cells.
  • processing chambers 710-720 are configured for depositing a thin film of lithium metal on the continuous sheet of material 750.
  • Any suitable lithium deposition process for depositing thin films of lithium metal may be used to deposit the thin film of lithium metal.
  • Deposition of the thin film of lithium metal may be by PVD processes, such as evaporation, a slot-die process, a transfer process, a lamination process or a three-dimensional lithium printing process.
  • the chambers for depositing the thin film of lithium metal may include a PVD system, such as an electron-beam evaporator, a thin film transfer system (including large area pattern printing systems such as gravure printing systems), a lamination system, or a slot-die deposition system.
  • the third processing chamber 730 is configured for depositing a lithium carbonate film on the metal film.
  • the lithium carbonate film may be deposited using a PVD sputtering technique as described herein.
  • the fourth processing chamber 740 is configured for forming a lithium halide film on the lithium carbonate film.
  • Any suitable lithium deposition process for depositing thin films of lithium metal may be used to deposit the thin film of lithium metal. Deposition of the thin film of lithium metal may be by PVD processes, such as evaporation, a slot-die process, a transfer process, a lamination process or a three- dimensional lithium printing process.
  • the fourth processing chamber 740 is an evaporation chamber or PVD chamber configured to deposit a PATENT Attorney Docket No.: 44020676WO01 lithium halide film over the continuous sheet of material 750.
  • the evaporation chamber has a processing region that is shown to comprise an evaporation source that may be placed in a crucible, which may be a thermal evaporator or an electron beam evaporator (cold) in a vacuum environment, for example.
  • the continuous sheet of material 750 is unwound from the feed reel 756 as indicated by the substrate movement direction shown by arrow 708.
  • the continuous sheet of material 750 may be guided via one or more auxiliary transfer reels 753a, 753b.
  • the continuous sheet of material 750 is guided by one or more substrate guide control units (not shown) that shall control the proper run of the flexible substrate, for instance, by fine adjusting the orientation of the flexible substrate.
  • the continuous sheet of material 750 is then moved through the deposition areas provided at the coating drum 755 and corresponding to positions of the deposition units 712, 722, 732, and 742. During operation, the coating drum 755 rotates around axis 751 such that the flexible substrate moves in the direction of arrow 708.
  • Figure 8 is a flow diagram of a method of forming a lithium metal anode 400 using a transfer substrate.
  • a second passivation layer is disposed over a transfer substrate (not shown).
  • the second passivation layer includes a dielectric film, such as a lithium halide film 320.
  • the lithium halide film 320 is selected from LiF, LiCl, LiBr, and LiI.
  • the lithium halide film 320 is a lithium fluoride film.
  • the lithium halide film 320 is deposited on the transfer substrate by Physical Vapor Deposition (PVD), evaporation, atomic layer deposition (ALD), a slot-die process, a thin-film transfer process, or a three-dimensional lithium printing process.
  • PVD is the method for deposition of the lithium halide film 320.
  • the lithium halide film 320 is deposited using a thermal evaporation process. In one embodiment, the lithium halide film is formed by reduction of a functional layer or surface functional groups on the plastic substrate used for metal deposition. This halide/organic layer will then be PATENT Attorney Docket No.: 44020676WO01 present on the metal film 450 surface following lamination to the substrate 460. In one embodiment, the lithium halide film 320 has a thickness of about 15 nm or less (e.g., from about 1 nm to about 15 nm; from about 5 to about 10 nm; from about 10 nm to about 15 nm).
  • the transfer substrate could be flexible plastic film (e.g., polyethylene terephthalate (PET), polyethylene (PE), polypropylene (PP), polyimide (PI), etc.).
  • the transfer substrate may be coated with an organic or inorganic functional layer or layers which may be selectively transferred or aid selective transfer of metal film (e.g., PDMS, boron nitride, aluminum oxide (AlO x ), polytetrafluoroethylene (PTFE), fluorinated ethylene propylene (FEP), perfluorooctanoic acid (PFOA), polyvinylidene (PVDF), etc.).
  • metal film e.g., PDMS, boron nitride, aluminum oxide (AlO x ), polytetrafluoroethylene (PTFE), fluorinated ethylene propylene (FEP), perfluorooctanoic acid (PFOA), polyvinylidene (PVDF), etc.
  • the metal and dielectric layers are then deposited onto this plastic substrate and subsequently transferred by lamination onto the desired device architecture, such as a current collector or substrate 460 (e.g., copper (Cu) and metallized plastic such as cu on PET).
  • the transfer substrate has a thickness of 200 microns or less, such as from 5 microns to about 100 microns, from about 10 microns to about 75 microns, or from about 20 microns to about 50 microns.
  • a first passivation layer is disposed over the second passivation layer.
  • the first passivation layer includes a lithium carbonate film 310.
  • the lithium carbonate film 310 has a thickness of about 200 nm or less (e.g., from about 5 nm to about 200 nm; from about 20 nm to about 150 nm; from about 40 nm to about 100 nm; from about 60 nm to about 80 nm). In one embodiment, the lithium carbonate film 310 (has a thickness of about 200 nm or less (e.g., from about 5 nm to about 200 nm; from about 20 nm to about 150 nm; from about 40 nm to about 100 nm; from about 60 nm to about 80 nm). [0072] At optional operation 806, a third passivation layer is disposed over the first passivation layer.
  • the third passivation layer includes a lithium oxide film.
  • the lithium oxide film 210 is formed by depositing an additional metal film via PVD in an oxygen-and-carbon-containing atmosphere.
  • the lithium oxide film 210 has a thickness of 500 nanometers or less (e.g., from about 1 nm to about 400 nm; from about 25 nm to about 300 nm; from about 50 nm to about 200 nm; or from PATENT Attorney Docket No.: 44020676WO01 about 100 nm to about 150 nm).
  • the lithium oxide film 210 is formed by depositing an additional metal film via PVD in an oxygen-containing atmosphere.
  • a metal film 450 is disposed over the first passivation layer.
  • the metal film 450 is the anode film 150.
  • the metal film is disposed over the lithium oxide film 210.
  • Deposition of the metal film 450 may be by evaporation, a sputtering process, a slot-die process, a transfer process, or a three-dimensional lithium printing process.
  • the chamber for depositing the metal film 450 may include a PVD system, an electron-beam evaporator, a thermal evaporator, a thin film transfer system (including large area pattern printing systems such as gravure printing systems) or a slot-die deposition system.
  • the metal film 450 has a thickness of 100 micrometers or less (e.g., from about 1 ⁇ m to about 100 ⁇ m; from about 3 ⁇ m to about 30 ⁇ m; from about 20 ⁇ m to about 30 ⁇ m; from about 1 ⁇ m to about 20 ⁇ m; or from about 50 ⁇ m to about 100 ⁇ m).
  • the films e.g., the first passivation layer, the second passivation layer, the third passivation layer, and the metal film
  • the films are transferred from the transfer substrate to the substrate 460.
  • the substrate 460 is the anode current collector 160.
  • the substrate 460 is a continuous sheet of material.
  • the substrate 460 includes one of aluminum (Al), copper (Cu), zinc (Zn), nickel (Ni), cobalt (Co), manganese (Mn), chromium (Cr), stainless steel, clad materials, alloys thereof, and combinations thereof.
  • the substrate 460 is perforated.
  • the substrate 460 may be of any form factor (e.g., metallic foil, sheet, or plate), shape and micro/macro structure.
  • the substrate 460 is exposed to a pretreatment process, which includes at least one of a plasma treatment or corona discharge process to remove organic materials from the exposed surfaces of the substrate 460. The pretreatment process is performed prior to film deposition on the substrate 460.
  • the foil was wound at a speed ranging from about 0.1 m/min to about 10 m/min.
  • the lithium coated substrate was wound past a modular gas showerhead, exposing the roll to carbon dioxide (CO 2 ) gas, leading to the formation of a lithium carbonate film, ranging in thickness from about 5 nm to about 20 nm.
  • Coated rolls were unloaded from the flexible substrate coating apparatus and A5 sheets of size 15 cm x 20 cm were cut and loaded into sample holders. Prepared samples were transferred to a toolset.
  • the toolset has process capabilities to accommodate resistive thermal evaporation, sputter deposition, electron beam evaporation, and ion assisted deposition.
  • Lithium halide films are grown by thermal evaporation both on the lithium metal coated substrates and, on a silicon wafer.
  • the substrate temperature was kept constant during deposition at about 25°C.
  • the starting material was ultra-high purity single crystal lithium halide powder, which is heated to about 800°C in an alumina crucible.
  • the evaporation rate monitored by a quartz oscillator, was kept at 1-2 ⁇ /s.
  • the vapor pressure in the deposition chamber was kept below 1 mPA.
  • Lithium halide samples has a thickness from about 1 nm to about 200 nm.
  • the composition of the SEI film stack was characterized using X-Ray Photoelectron Spectroscopy (XPS).
  • Coin cells were built consisting of modified lithium on copper (5 ⁇ m lithium, 18 ⁇ m copper, 1 cm 2 ), double polymer separator (Celgard 2400) and 60 ⁇ L of 1M LiPF 6 with 2% FEC in 1:1 EC:EMC as electrolyte.
  • Potentiostatic electrochemical impedance spectroscopy (PEIS) was conducted at 5 mV in the frequency range of about 1 MHz to about 10 mHz, 2 hours after the assembly of the cells.
  • Direct current internal resistance (DCIR) measurements were done at currents from about 0.2 mA to about 3 mA in steps of 0.2 mA. Each current pulse is 10 seconds and there is a 15 minute rest between two pulses.
  • FIG. 10 illustrates a modified interface lithium metal anode 1000.
  • the modified interface lithium metal anode 1000 includes a separator film 1030, a first side first passivation layer 1010a, a second side first passivation layer 1010b, a first side second passivation layer 1020a, a second side second passivation layer 1020b, a first side metal film 1060a, and a second side metal film 1060b.
  • the first side and second side passivation layers 1010a, 1010b are disposed on a first side and a second side of the separator film 1030, respectively.
  • the first side and the second side second passivation layers 1020a, 1020b are disposed on the first side and second side first passivation layers 1010a, 1010b, respectively.
  • the first side and second side metal films 1060a, 1060b are disposed on the first side and the second side second passivation layers 1020a, 1020b, respectively.
  • the lithium carbonate/lithium halide PATENT Attorney Docket No.: 44020676WO01 SEI film stack are deposited by PVD directly on to lithium metal prior to use in a deposition stripping cycle.

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  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
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  • Battery Electrode And Active Subsutance (AREA)

Abstract

Des modes de réalisation de la présente invention comprennent une anode pour une batterie comprenant un substrat, un film métallique disposé sur le substrat, et un empilement de films disposé sur le film métallique. L'empilement de films comprend un film de carbonate de lithium et un film d'halogénure de lithium disposé sur le carbonate de lithium. Le film de carbonate de lithium est disposé sur le film métallique.
PCT/US2023/034042 2022-09-28 2023-09-28 Réduction d'oxyde et d'hydroxyde de métal alcalin dans le film par couche passivée de surface ex situ WO2024073001A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005142156A (ja) * 2003-10-31 2005-06-02 Samsung Sdi Co Ltd リチウム金属二次電池用負極及びその製造方法並びにそれを含むリチウム金属二次電池
JP2009544121A (ja) * 2006-07-18 2009-12-10 イドロ−ケベック 活性リチウムをベースとする多層材料、調製方法、および電気化学的発電装置における応用
WO2014142953A1 (fr) * 2013-03-15 2014-09-18 Sion Power Corporation Structures protectrices pour électrodes
KR20160037636A (ko) * 2014-09-29 2016-04-06 주식회사 엘지화학 패시베이션층이 형성된 리튬 전극 구조체 및 그 제조 방법
WO2021120927A1 (fr) * 2019-12-16 2021-06-24 比亚迪股份有限公司 Matériau de compensation de lithium et son procédé de préparation, électrode négative et batterie au lithium-ion

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005142156A (ja) * 2003-10-31 2005-06-02 Samsung Sdi Co Ltd リチウム金属二次電池用負極及びその製造方法並びにそれを含むリチウム金属二次電池
JP2009544121A (ja) * 2006-07-18 2009-12-10 イドロ−ケベック 活性リチウムをベースとする多層材料、調製方法、および電気化学的発電装置における応用
WO2014142953A1 (fr) * 2013-03-15 2014-09-18 Sion Power Corporation Structures protectrices pour électrodes
KR20160037636A (ko) * 2014-09-29 2016-04-06 주식회사 엘지화학 패시베이션층이 형성된 리튬 전극 구조체 및 그 제조 방법
WO2021120927A1 (fr) * 2019-12-16 2021-06-24 比亚迪股份有限公司 Matériau de compensation de lithium et son procédé de préparation, électrode négative et batterie au lithium-ion

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